WO2011040248A1 - Composition de résine photosensible positive, film durci obtenu à l'aide de celle-ci et dispositif optique - Google Patents

Composition de résine photosensible positive, film durci obtenu à l'aide de celle-ci et dispositif optique Download PDF

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Publication number
WO2011040248A1
WO2011040248A1 PCT/JP2010/066021 JP2010066021W WO2011040248A1 WO 2011040248 A1 WO2011040248 A1 WO 2011040248A1 JP 2010066021 W JP2010066021 W JP 2010066021W WO 2011040248 A1 WO2011040248 A1 WO 2011040248A1
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mol
general formula
organosilane
compound
resin composition
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PCT/JP2010/066021
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English (en)
Japanese (ja)
Inventor
鴨川政雄
岡沢徹
諏訪充史
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東レ株式会社
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Priority to CN2010800363594A priority Critical patent/CN102472964B/zh
Priority to US13/496,717 priority patent/US8828642B2/en
Priority to KR1020127001343A priority patent/KR101726897B1/ko
Priority to JP2011534190A priority patent/JP5423802B2/ja
Priority to EP10820367.0A priority patent/EP2485091B1/fr
Publication of WO2011040248A1 publication Critical patent/WO2011040248A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making

Definitions

  • the present invention relates to a positive photosensitive resin composition, a cured film using the same, and an optical device.
  • a positive photosensitive resin composition for example, Patent Document 1 containing an alkali-soluble polymer such as polyamic acid, a compound having a phenolic hydroxyl group, a quinonediazide compound and inorganic particles, or a silyl having a phenol unit.
  • an alkali-soluble polymer such as polyamic acid, a compound having a phenolic hydroxyl group, a quinonediazide compound and inorganic particles, or a silyl having a phenol unit.
  • a silicone copolymer having a sesquioxane and a condensed polycyclic hydrocarbon group for example, see Patent Document 2
  • the photosensitive resin compositions and polymers disclosed in these publications have a problem of insufficient transparency due to coloring of polyamic acid or phenolic hydroxyl group.
  • a material containing a siloxane compound having excellent transparency a photosensitive siloxane composition containing a polysiloxane, a quinonediazide compound, a solvent and a thermally crosslinkable compound (for example, see Patent Document 3), or a siloxane having an aromatic hydrocarbon group
  • Patent Document 4 a high refractive index material containing a compound
  • Patent Document 4 a material capable of forming a cured film having a higher refractive index has been demanded.
  • a siloxane-based resin composition obtained by a method of hydrolyzing and condensing alkoxysilane in the presence of metal compound particles is disclosed.
  • a resin composition has insufficient sensitivity at the time of exposure, and a minute amount of undissolved residue is generated at the time of development, so that the resolution is not sufficient.
  • An object of the present invention is to provide a positive photosensitive resin composition excellent in sensitivity and resolution without impairing properties of high refractive index and high transparency.
  • the present invention has the following configuration. Namely, (a) polysiloxane synthesized by hydrolyzing and partially condensing organosilane and organosilane oligomer represented by the following general formula (1), (b) aluminum compound particles, tin compound particles, titanium compound Particles, zirconium compound particles, composite particles thereof or composite particles of any of these with a silicon compound, (c) a naphthoquinonediazide compound and (d) a solvent, wherein the organosilane oligomer is represented by the following general formula (2) A positive photosensitive resin composition comprising an organosilane.
  • (a ′) represented by the following general formula (1) in the presence of aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles, composite particles thereof, or composite particles of any of these and silicon compounds.
  • a positive photosensitive resin composition comprising an organosilane represented by 2).
  • R 1 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • R 2 represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • n represents an integer of 0 to 3. When n is 2 or more, the plurality of R 1 may be the same or different from each other. When n is 2 or less, the plurality of R 2 may be the same or different.
  • R 3 to R 6 each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • m represents a range of 2 to 8. When m is 2 or more, the plurality of R 4 and R 5 may be the same or different.
  • a positive photosensitive resin composition having high sensitivity and resolution, and capable of obtaining a cured film having a high refractive index and high transparency.
  • the organosilane oligomer contains an organosilane represented by the general formula (2).
  • the second embodiment of the positive photosensitive resin composition of the present invention is as follows: (a ′) aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles, composite particles thereof, or any of these and a silicon compound And (c) naphthoquinonediazide compound synthesized by hydrolyzing and partially condensing organosilane and organosilane oligomer represented by the following general formula (1) in the presence of composite particles And (d) a solvent, and the organosilane oligomer includes an organosilane represented by the general formula (2).
  • R 1 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • R 2 represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • n represents an integer of 0 to 3. When n is 2 or more, the plurality of R 1 may be the same or different from each other. When n is 2 or less, the plurality of R 2 may be the same or different.
  • R 3 to R 6 each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • m represents a range of 2 to 8. When m is 2 or more, the plurality of R 4 and R 5 may be the same or different.
  • R 1 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • R 1 of each may be the same or different.
  • R 2 represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms, and when n is 2 or less, the plurality of R 2 are the same But it may be different.
  • any of the alkyl group, alkenyl group, aryl group, and acyl group may be substituted.
  • substituents include a hydroxy group, an alkoxy group, an epoxy group, an oxetanyl group, a fluoro group, an amino group, a mercapto group, Examples thereof include an isocyanate group, an acryloxy group, a methacryloxy group, and a carboxy group.
  • the carbon number of the alkyl group, alkenyl group, aryl group, and acyl group does not include the carbon number contained in the substituent.
  • alkyl group and its substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, [(3-ethyl-3-oxetanyl) methoxy] propyl group, 3- Examples include aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group and the like.
  • alkenyl group and substituted products thereof include a vinyl group.
  • aryl group and its substituent include a phenyl group, a tolyl group, a p-hydroxyphenyl group, a naphthyl group which is a condensed polycyclic aromatic hydrocarbon group, a phenanthrenyl group, a fluorenyl group, a pyrenyl group, an indenyl group, An acenaphthenyl group etc. are mentioned.
  • Specific examples of the acyl group and substituted products thereof include an acetyl group.
  • R 1 in the general formula (1) contains an aryl group having 6 to 16 carbon atoms.
  • the content of Si atoms bonded to R 1 which is an aryl group in the polysiloxane (a) is preferably 30 mol% or more, more preferably 40 mol, based on the total content of Si atoms derived from organosilane. % Or more. Containing 30 mol% or more suppresses phase separation between (a) polysiloxane and (c) naphthoquinonediazide compound in coating, drying, thermosetting processes, etc. at the time of preparing a cured film, and facilitates uniform cured film Can be formed.
  • part or all of the aryl group is a condensed polycyclic aromatic hydrocarbon group.
  • a condensed polycyclic aromatic hydrocarbon group having a high ⁇ electron density By containing a condensed polycyclic aromatic hydrocarbon group having a high ⁇ electron density, a cured film can have a high refractive index.
  • the effect of inhibiting dissolution of the unexposed portion is developed during development due to the interaction with naphthoquinonediazide, the contrast between the exposed portion and the unexposed portion is increased.
  • the sensitivity can be further improved, and further, a reduction in resolution due to a minute undissolved residue can be suppressed.
  • the condensed polycyclic aromatic hydrocarbon group a naphthyl group is preferable.
  • the content of Si atoms bonded to R 1 which is a condensed polycyclic aromatic hydrocarbon group is 10 mol% or more in the total content of Si atoms derived from organosilane. Is preferred.
  • the sensitivity and resolution of the positive photosensitive resin composition can be further improved, and the refractive index of the cured film can be further improved.
  • 60 mol% or less is preferable and 50 mol% or less is more preferable from the viewpoint of suppressing minute dissolution residue during development and further improving the resolution of the positive photosensitive resin composition.
  • the content of Si atom bonded to R 1 which is a condensed polycyclic aromatic hydrocarbon group was determined by measuring the 29 Si-NMR spectrum of polysiloxane, and the peak area of Si bonded with the condensed polycyclic aromatic hydrocarbon group And the ratio of the peak area of Si to which the condensed polycyclic aromatic hydrocarbon group is not bonded.
  • n an integer of 0 to 3.
  • organosilane represented by the general formula (1) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, de
  • organosilanes Two or more of these organosilanes may be used.
  • trifunctional silanes are preferably used from the viewpoint of improving the hydrolyzability / condensation reactivity at the time of polysiloxane synthesis and further improving the crack resistance and hardness of the cured film.
  • R 1 is a condensed polycyclic aromatic hydrocarbon group such as 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthraceni Rutrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 2-fluorenonyltrimethoxysilane, 1-pyre Nyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acenaphthenyltrimethoxysilane and the like are preferable.
  • R 3 to R 6 each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • R 4 and R 5 may be the same or different. Any of the alkyl group, the acyl group, and the aryl group may be substituted, and specific examples of the substituent include the groups described as specific examples of the substituent for R 2 . Specific examples of the alkyl group, acyl group, aryl group, and substituted products thereof include the groups described as specific examples of R 2 . Of these, alkyl groups having 1 to 6 carbon atoms are preferred.
  • the positive photosensitive resin composition of the present invention exhibits alkali solubility due to silanol groups generated by hydrolysis of organosilane. Since the silanol group disappears due to condensation, the conventionally known polysiloxane becomes difficult to dissolve in alkali when the condensation is advanced, and the sensitivity may be lowered or the resolution may be lowered due to a small amount of undissolved residue. On the other hand, when the condensation is insufficient, the glass transition point of the polysiloxane is lowered, and there is a case where the resolution is lowered by inducing pattern dripping in the curing. In this invention, many silanol groups arise by hydrolyzing using the organosilane represented by General formula (2).
  • silanol groups are present at positions close to each other, so that the interaction with the (c) naphthoquinonediazide compound described later increases. As a result, the contrast between the exposed and unexposed areas is increased, so that the sensitivity can be further improved, and further, a reduction in resolution due to a minute undissolved residue can be suppressed.
  • organosilane represented by the general formula (2) examples include methyl silicate 51 (R 3 to R 6 : methyl group, m: average 4) manufactured by Fuso Chemical Industry Co., Ltd., M manufactured by Tama Chemical Industry Co., Ltd.
  • Silicate 51 (R 3 to R 6 : methyl group, m: average 3 to 5), silicate 40 (R 3 to R 6 : ethyl group, m: average 4 to 6), silicate 45 (R 3 to R 6 : ethyl) Group, m: average 6 to 8), methyl silicate 51 (R 3 to R 6 : methyl group, m: average 4) manufactured by Colcoat Co., Ltd., methyl silicate 53A (R 3 to R 6 : methyl group, m: average 7) ), Ethyl silicate 40 (R 3 to R 6 : ethyl group, m: average 5), and the like. Two or more of these may be used.
  • the content of Si atoms derived from the organosilane represented by the general formula (2) in the organosilane oligomer in the polysiloxane is (a) the total content of Si atoms derived from the organosilane oligomer in the polysiloxane. It is preferable that it is 67 mol% or more and 100 mol% or less. By containing 67 mol% or more of Si atoms derived from the organosilane represented by the general formula (2), the sensitivity and resolution of the resulting positive photosensitive resin composition can be further improved. 80 mol% or more is more preferable, and 100 mol% is most preferable.
  • polysiloxane synthesized by hydrolyzing and partially condensing the organosilane represented by the general formula (1) and the organosilane represented by the general formula (2) is most preferable. Moreover, by containing 100 mol% or less, generation
  • combination can be suppressed, and the coating film property of the positive photosensitive resin composition obtained can be improved.
  • the content of Si atoms derived from the organosilane represented by the general formula (2) in the polysiloxane is 5 mol% or more and 50 mol% or less in the total Si atom content derived from the organosilane. preferable.
  • the sensitivity and resolution of the resulting positive photosensitive resin composition can be further improved. 10 mol% or more is more preferable.
  • combination can be suppressed by containing 50 mol% or less, and the coating film property of the positive photosensitive resin composition obtained can be improved.
  • the content of Si atoms derived from the organosilane represented by the general formula (2) in the polysiloxane is determined by 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF-MS, etc.
  • the structure of the organosilane to be obtained can be determined and obtained from the integration ratio of the peak derived from the Si—C bond and the peak derived from the Si—O bond in the IR spectrum.
  • the weight average molecular weight (Mw) of the polysiloxane is not particularly limited, but is preferably 1,000 or more in terms of polystyrene measured by GPC (gel permeation chromatography), and the coating properties are improved. On the other hand, from the viewpoint of solubility in a developer, it is preferably 100,000 or less, and more preferably 50,000 or less.
  • the polysiloxane in the present invention is synthesized by hydrolyzing and partially condensing the organosilane represented by the general formula (1) and the organosilane oligomer.
  • the said organosilane oligomer contains the organosilane represented by the said General formula (2).
  • partial condensation refers to not allowing all of the hydrolyzate Si—OH to be condensed, but partially leaving Si—OH in the resulting polysiloxane. In general condensation conditions described later, it is common that Si—OH partially remains. In the present invention, the amount of Si—OH remaining is not limited.
  • other organosilanes may be used.
  • a general method can be used for hydrolysis and partial condensation. For example, a method of adding a solvent, water and, if necessary, a catalyst to the organosilane mixture and heating and stirring at 50 to 150 ° C. for about 0.5 to 100 hours can be mentioned. During the stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.
  • the solvent is not particularly limited, but (d) a solvent described later is generally used.
  • the amount of the solvent added is preferably 10 to 1,000 parts by weight with respect to 100 parts by weight of the organosilane.
  • the amount of water used for the hydrolysis reaction is preferably 0.5 to 2 mol with respect to 1 mol of the hydrolyzable group.
  • the catalyst is not particularly limited, but an acid catalyst and a base catalyst are preferably used.
  • the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or anhydride thereof, ion exchange resin, and the like.
  • Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino Examples include alkoxysilanes having groups and ion exchange resins.
  • the addition amount of the catalyst is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the organosilane.
  • the polysiloxane solution after hydrolysis and partial condensation does not contain the catalyst, and the catalyst can be removed as necessary. it can.
  • the removal method is not particularly limited, but water washing and / or treatment with an ion exchange resin is preferable from the viewpoint of easy operation and removability.
  • Water washing is a method of concentrating an organic layer obtained by diluting a polysiloxane solution with an appropriate hydrophobic solvent and then washing several times with water with an evaporator or the like.
  • the treatment with an ion exchange resin is a method in which a polysiloxane solution is brought into contact with an appropriate ion exchange resin.
  • the positive photosensitive resin composition of the present invention comprises (b) aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles, composite particles thereof or composite particles of any of these and a silicon compound (hereinafter referred to as metal).
  • metal compound particles include metal compounds such as oxides, sulfides and hydroxides of aluminum, tin, titanium or zirconium, and composite particles of these metal compounds and silicon compounds.
  • composite particles of a metal compound and a silicon compound include silicon oxide-metal compound composite particles obtained by synthesizing metal particles in the presence of a silicon oxide compound, and silane surface-coated metal compound particles obtained by reacting metal particles with a silane coupling agent. Can be mentioned. Two or more of these may be contained.
  • the metal compound particles as described above, the cured film can have a high refractive index.
  • metal compound particles include tin oxide-titanium oxide composite particles “OPTRAIK (registered trademark)” TR-502, “OPTRAIK” TR-504, and silicon oxide-titanium oxide composite particles “OPT”. Lake “TR-503", “Optlake” TR-513, “Optlake” TR-520, “Optlake” TR-527, “Optrake” TR-528, “Optlake” TR-529, “Optrake” TR-543, “OPTRAIK” TR-544, titanium oxide particle "OPTRAIK” TR-505 (trade name, manufactured by JGC Catalysts & Chemicals Co., Ltd.), zirconium oxide particles (high purity chemical research) ), Tin oxide-zirconium oxide composite particles (manufactured by JGC Catalysts & Chemicals Co., Ltd.), tin oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.), etc. .
  • the content of the (b) metal compound particles is preferably 10 parts by weight or more, more preferably 25 parts by weight or more with respect to 100 parts by weight of the polysiloxane of the component (a). Moreover, 250 weight part or less is preferable and 200 weight part or less is more preferable. Within this range, the transmittance and refractive index of the cured film can be further improved while maintaining the high sensitivity and resolution of the positive photosensitive resin composition.
  • an aluminum compound particle, a tin compound particle, a titanium compound particle, a zirconium compound particle, a composite particle thereof, or a composite particle of any one of these and a silicon compound is represented by the general formula (1).
  • the metal compound particle-containing polysiloxane synthesized by hydrolyzing and partially condensing the organosilane and the organosilane oligomer will be described.
  • the said organosilane oligomer contains the organosilane represented by the said General formula (2).
  • the metal compound particles used in the metal compound particle-containing polysiloxane are the same as the metal compound particles exemplified as the component (b).
  • the organosilane represented by the general formula (1) or (2) is the same as the organosilane exemplified for the polysiloxane of the component (a).
  • content of Si atom originating in the organosilane represented by the said General formula (2) in the said organosilane oligomer is 67 mol% or more and 100 mol% or less in Si atom total content originating in an organosilane oligomer. It is preferable.
  • the sensitivity and resolution of the resulting positive photosensitive resin composition can be further improved. 80 mol% or more is more preferable, and 100 mol% or more is most preferable. That is, (a ′) represented by the general formula (1) in the presence of aluminum compound particles, tin compound particles, titanium compound particles, zirconium compound particles, composite particles thereof, or composite particles of any of these and a silicon compound.
  • the metal compound particle-containing polysiloxane synthesized by hydrolyzing and partially condensing the organosilane and the organosilane represented by the general formula (2) is most preferable.
  • the sensitivity and resolution of the resulting positive photosensitive resin composition can be further improved. 10 mol% or more is more preferable. Moreover, generation
  • combination can be suppressed by containing 50 mol% or less, and the coating film property of the positive photosensitive resin composition obtained can be improved.
  • the content of Si atoms derived from the organosilane represented by the general formula (2) in the (a ′) metal compound-containing polysiloxane can be determined in the same manner as the polysiloxane of the component (a).
  • the content of Si atom bonded to R 1 which is a condensed polycyclic aromatic hydrocarbon group can be determined in the same manner as the polysiloxane of component (a).
  • the metal compound particle polysiloxane in the present invention is synthesized by hydrolyzing and partially condensing the organosilane in the presence of the metal compound particle. Preferred reaction conditions in the hydrolysis and partial condensation are the same as in the case of the polysiloxane (a).
  • the positive photosensitive resin composition of the present invention contains (c) a naphthoquinonediazide compound.
  • a naphthoquinonediazide compound By containing a naphthoquinonediazide compound, the photosensitivity in which the exposed portion is removed with a developer is exhibited.
  • the naphthoquinone diazide compound a compound in which naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group is preferable.
  • Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all manufactured by Honshu Chemical Industry Co., Ltd.).
  • the naphthoquinone diazide compound can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinone diazide sulfonic acid chloride.
  • a compound having a phenolic hydroxyl group and naphthoquinone diazide sulfonic acid chloride.
  • the naphthoquinone diazide sulfonic acid chloride used as a raw material 4-naphthoquinone diazide sulfonic acid chloride or 5-naphthoquinone diazide sulfonic acid chloride can be used. Since 4-naphthoquinonediazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure.
  • the 5-naphthoquinonediazide sulfonic acid ester compound has absorption in a wide wavelength range and is therefore suitable for exposure in a wide wavelength range. It is preferable to select a 4-naphthoquinone diazide sulfonic acid ester compound or a 5-naphthoquinone diazide sulfonic acid ester compound depending on the wavelength to be exposed. A combination of 4-naphthoquinone diazide sulfonic acid ester compound and 5-naphthoquinone diazide sulfonic acid ester compound can also be used.
  • the content of the (c) naphthoquinonediazide compound in the positive photosensitive resin composition of the present invention is not particularly limited, but it is 1 per 100 parts by weight of (a) polysiloxane or (a ′) metal compound particle-containing polysiloxane. Part by weight or more is preferable, and 3 parts by weight or more is more preferable. In addition, from the viewpoint of suppressing the decrease in compatibility with polysiloxane and coloring due to decomposition during thermosetting, and further improving the transparency of the positive photosensitive resin composition and the cured film, 30 parts by weight or less is preferable. More preferred are parts by weight or less.
  • the positive photosensitive resin composition of the present invention contains (d) a solvent.
  • a solvent Although there is no restriction
  • a solvent having an alcoholic hydroxyl group is used, the solubility of (a) polysiloxane or (a ′) metal compound particle-containing polysiloxane and (c) quinonediazide compound is improved, and it can be obtained from a positive photosensitive resin composition.
  • the transparency of the coating film can be further improved.
  • the solvent having an alcoholic hydroxyl group is not particularly limited, but a compound having a boiling point of 110 to 250 ° C. under atmospheric pressure is preferable.
  • the boiling point is 110 ° C. or higher, drying during the formation of the coating film proceeds moderately, and a coating film with a good surface appearance can be easily obtained.
  • the boiling point is 250 ° C. or lower, the solvent can be easily removed.
  • solvents may be contained together with or in place of the above solvents.
  • Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1- Esters such as butyl acetate and ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone, ethers such as diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether and diethylene glycol dimethyl ether ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone
  • the content of the (d) solvent in the positive photosensitive resin composition of the present invention but preferably (a) polysiloxane or (a ′) 100 parts by weight of polysiloxane containing metal compound particles. The range is from 100 to 2,000 parts by weight.
  • UV-visible exposure machine such as a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA), etc., and pattern about 10 to 4000 J / m 2 (wavelength 365 nm exposure dose conversion) through the desired mask Exposure.
  • the exposed area is dissolved and removed by development to obtain a positive pattern.
  • the resolution of the pattern is preferably 8 ⁇ m or less.
  • a developing method it is preferable to immerse in a developing solution for 5 seconds to 10 minutes by a method such as showering, dipping, or paddle.
  • the developer a known alkali developer can be used.
  • inorganic alkali such as alkali metal hydroxide, carbonate, phosphate, silicate, borate, 2-diethylaminoethanol, mono Examples include amines such as ethanolamine and diethanolamine, and aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH) and choline. Two or more of these may be used.
  • TMAH tetramethylammonium hydroxide
  • two or more of these may be used.
  • it is preferable to rinse with water after development, and if necessary, dehydration drying baking may be performed at a temperature range of 50 to 150
  • the entire surface is preferably exposed (bleaching exposure) by about 100 to 20,000 J / m 2 (wavelength 365 nm exposure amount conversion) using an ultraviolet-visible exposure machine such as PLA.
  • bleaching exposure the unreacted naphthoquinonediazide compound remaining in the development film can be photodecomposed, and the transparency of the resulting cured film can be further improved.
  • the film subjected to bleaching exposure is heated (soft bake) for 30 seconds to 30 minutes in a temperature range of 50 to 250 ° C with a heating device such as a hot plate or oven, if necessary, and then heated in a hot plate or oven.
  • a cured film is obtained by heating (curing) in a temperature range of 150 to 450 ° C. for about 30 seconds to 2 hours.
  • the positive photosensitive resin composition of the present invention from the viewpoint of productivity in the pattern formation, it is preferable that the sensitivity at the time of exposure is 1500 J / m 2 or less, more preferably 1000 J / m 2 or less.
  • Such a high sensitivity can be easily obtained by, for example, a positive photosensitive resin composition containing polysiloxane using an organosilane represented by the general formula (2).
  • the sensitivity at the time of exposure is obtained by the following method.
  • the positive photosensitive resin composition is spin-coated on a silicon wafer at an arbitrary rotation number using a spin coater, and prebaked at 120 ° C. for 3 minutes using a hot plate to prepare a prebaked film having a thickness of 1 ⁇ m.
  • PLA PLA-501F manufactured by Canon Inc.
  • the pre-baked film is exposed through a gray scale mask having a line and space pattern of 1 to 10 ⁇ m for sensitivity measurement with an ultra-high pressure mercury lamp, and then automatically developed.
  • the positive photosensitive resin composition of the present invention preferably has a cured resolution of 10 ⁇ m or less, more preferably 5 ⁇ m or less in order to form a fine hole pattern.
  • Such resolution can be easily obtained by, for example, a positive photosensitive resin composition containing polysiloxane using an organosilane represented by the general formula (2).
  • the resolution after curing is obtained by the following method. Similar to the above-described method for obtaining the sensitivity at the time of exposure, an exposure amount for resolving a 10 ⁇ m line-and-space pattern with a one-to-one width is obtained as sensitivity. Thereafter, soft baking is performed at 200 ° C. for 5 minutes using a hot plate, and then cured at 300 ° C. for 5 minutes using a hot plate to produce a cured film, and the minimum pattern dimension in sensitivity is obtained as the post-curing resolution.
  • the cured film obtained by curing the positive photosensitive resin composition of the present invention preferably has a light transmittance of 90% or more per film thickness of 1 ⁇ m at a wavelength of 400 nm, more preferably 92% or more.
  • a high transmittance can be easily obtained by, for example, a positive photosensitive resin composition using a highly transparent polysiloxane as a resin component.
  • the transmittance per 1 ⁇ m of film thickness at a wavelength of 400 nm of the cured film is determined by the following method.
  • the positive photosensitive resin composition is spin-coated on a Tempax glass plate at an arbitrary rotation number using a spin coater, and prebaked at 120 ° C. for 2 minutes using a hot plate. Then, as bleaching exposure, using PLA, the whole surface of the film was exposed to an ultrahigh pressure mercury lamp at 5000 mJ / m 2 (wavelength 365 nm exposure amount conversion) and thermally cured at 300 ° C. for 5 minutes in the air using a hot plate. A cured film having a thickness of 1 ⁇ m is prepared.
  • the positive photosensitive resin composition and the cured film of the present invention are suitably used for optical devices such as a solid-state imaging device, an optical filter, and a display. More specifically, condensing microlenses and optical waveguides formed on solid-state image sensors, antireflection films installed as optical filters, flattening materials for display TFT substrates, protective films for liquid crystal displays and color filters And a phase shifter. Among these, since high transparency and a high refractive index can be achieved at the same time, it is particularly suitably used as a condensing microlens formed on a solid-state image sensor, or an optical waveguide connecting the condensing microlens and the optical sensor unit. .
  • the solid content concentration of the polysiloxane solution was determined by the following method. 1.5 g of the polysiloxane solution was weighed in an aluminum cup and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid. The solid content remaining in the heated aluminum cup was weighed to determine the solid content concentration of the polysiloxane solution.
  • the Si atom content derived from the organosilane represented by the general formula (2) in the polysiloxane or metal compound particle-containing polysiloxane was determined by the following method. Assuming that the organosilane used was completely condensed, the amount of Si—O containing no Si—C was calculated from the integral ratio of the peak derived from the Si—C bond and the peak derived from the Si—O bond in the IR spectrum, Thereby, the Si atom content derived from the organosilane represented by the general formula (2) was determined.
  • the content of Si atom bonded to R 1 which is a condensed polycyclic aromatic hydrocarbon group in polysiloxane or metal compound particle-containing polysiloxane was measured by 29 Si-NMR spectrum of polysiloxane or metal compound particle-containing polysiloxane.
  • the ratio of the peak area of Si to which the condensed polycyclic aromatic hydrocarbon group was bonded to the peak area of Si to which the condensed polycyclic aromatic hydrocarbon group was not bonded was obtained.
  • the weight average molecular weight (Mw) of the obtained trifunctional silane oligomer was measured using GPC (Gel Permeation Chromatography) HLC-8220 (manufactured by Tosoh Corporation) as the developing solvent, and the weight average in terms of polystyrene. Molecular weight (Mw) was calculated.
  • PS-1 Synthesis of Polysiloxane Solution
  • Synthesis Example 3 Synthesis of Polysiloxane Solution (PS-3) In a 500 ml three-necked flask, 27.24 g (0.20 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 12.32 g (0.05 mol), M silicate 51 (manufactured by Tama Chemical Co., Ltd.), 29.38 g (corresponding to 0.25 mol of Si atom moles), and PGMEA, 152.
  • PS-3 Synthesis of Polysiloxane Solution
  • PS-4 Polysiloxane Solution
  • PS-5 49.58 g (0.25 mol) of phenyltrimethoxysilane and 12.32 g of 2- (3
  • PS-6 Polysiloxane solution
  • PS-7 Polysiloxane solution
  • PS-8 Poly
  • polysiloxane solution PS-8
  • a total of 97.58 g of methanol and water as by-products were distilled out.
  • the resulting polysiloxane solution (PS-8) had a solid content concentration of 40% by weight.
  • Si atom content originating in the organosilane represented by General formula (2) in polysiloxane was 12.4 mol%.
  • the content of Si atoms bonded to the condensed polycyclic aromatic hydrocarbon group in the polysiloxane was 14.0 mol%.
  • polysiloxane solution PS-9
  • a total of 97.58 g of methanol and water as by-products were distilled out.
  • the resulting polysiloxane solution (PS-9) had a solid content concentration of 40% by weight.
  • Si atom content originating in the organosilane represented by General formula (2) in polysiloxane was 12.4 mol%.
  • the content of Si atoms bonded to the condensed polycyclic aromatic hydrocarbon group in the polysiloxane was 28.0 mol%.
  • Synthesis Example 10 Synthesis of polysiloxane solution (PS-10) 40.86 g (0.30 mol) of methyltrimethoxysilane and 12.32 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane in a 500 ml three-necked flask (0.05 mol), 124.18 g (0.50 mol) of naphthyltrimethoxysilane, 17.65 g of M silicate 51 (manufactured by Tama Chemical Co., Ltd.) (equivalent to 0.15 mol of Si atoms), and PGMEA of 184.
  • PS-10 polysiloxane solution
  • PS-10 40.86 g (0.30 mol) of methyltrimethoxysilane and 12.32 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane in a 500 ml three-necked flask (0.05
  • Si atom content originating in the organosilane represented by General formula (2) in polysiloxane was 12.4 mol%. Further, the content of Si atoms bonded to the condensed polycyclic aromatic hydrocarbon group in the polysiloxane was 46.7 mol%.
  • Synthesis Example 11 Synthesis of Polysiloxane Solution (PS-11) In a 500 ml three-necked flask, 13.62 g (0.10 mol) of methyltrimethoxysilane and 12.32 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (0.05 mol), 178.85 g (0.70 mol) of naphthyltrimethoxysilane, 17.65 g of M silicate 51 (manufactured by Tama Chemical Co., Ltd.) (corresponding to 0.15 mol of Si atoms), and PGMEA of 212.
  • PS-11 Synthesis of Polysiloxane Solution (PS-11) In a 500 ml three-necked flask, 13.62 g (0.10 mol) of methyltrimethoxysilane and 12.32 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (0.05
  • a 10 g charge (initial monomer concentration 50.6% by weight), and an aqueous phosphoric acid solution prepared by dissolving 0.109 g of phosphoric acid (0.05% by weight with respect to the charged monomer) in 53.55 g of water while stirring at room temperature for 10 minutes Added over time. Thereafter, the mixture was heated and stirred in the same manner as in Synthesis Example 1 to obtain a polysiloxane solution (PS-11). During the reaction, a total of 97.58 g of methanol and water as by-products were distilled out. The resulting polysiloxane solution (PS-11) had a solid content concentration of 40% by weight.
  • Si atom content originating in the organosilane represented by General formula (2) in polysiloxane was 12.4 mol%. Further, the content of Si atom bonded to the condensed polycyclic aromatic hydrocarbon group in the polysiloxane was 65.3 mol%.
  • PS-12 Polysiloxane Solution
  • Synthesis Example 13 Synthesis of Polysiloxane Solution (PS-13) In a 500 ml three-necked flask, 40.86 g (0.30 mol (number of moles of silane atoms: 0.30 mol)) of methyltrimethoxysilane and 99.15 g of phenyltrimethoxysilane ( 0.50 mol (0.50 mol of silane atoms), 12.32 g (0.05 mol (0.05 mol of silane atoms)), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, linear 11.38 g of Silanol-terminated polydimethylsiloxane DMS-S12 (Mw: 400 to 700) manufactured by Gelest Co.
  • PS-13 Polysiloxane Solution
  • a trifunctional silane oligomer solution (TS-1).
  • TS-1 trifunctional silane oligomer solution
  • Mw weight average molecular weight
  • a trifunctional silane oligomer solution (TS-1).
  • TS-1 trifunctional silane oligomer solution
  • Mw weight average molecular weight
  • a trifunctional silane oligomer solution (TS-3).
  • TS-3 trifunctional silane oligomer solution
  • Mw weight average molecular weight
  • Synthesis Example 24 Synthesis of naphthoquinonediazide compound (QD-2) 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 5-naphthoquinonediazidesulfonyl acid chloride 37 under a dry nitrogen stream .62 g (0.14 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature.
  • 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not exceed 35 ° C. It stirred at 30 degreeC after dripping for 2 hours.
  • the photosensitive properties and cured film properties of the compositions in the examples and comparative examples were evaluated by the following methods.
  • a silicon wafer substrate was used for the following evaluations (1) to (5), and a Tempax glass substrate was used for the evaluation (6).
  • (1) Measurement of film thickness Using Lambda Ace STM-602 (trade name, manufactured by Dainippon Screen), the thickness of the pre-baked film and the cured film was measured at a refractive index of 1.70.
  • (2) Calculation of remaining film rate The remaining film rate was calculated according to the following formula.
  • Residual film ratio (%) unexposed film thickness after development / film thickness after pre-baking ⁇ 100 (3) Calculation of photosensitivity After development, an exposure amount (hereinafter referred to as an optimum exposure amount) for forming a 10 ⁇ m line-and-space pattern in a one-to-one width was defined as photosensitivity. (4) Calculation of resolution The minimum pattern size after development at the optimum exposure amount was taken as post-development resolution, and the minimum pattern size after cure was taken as post-cure resolution.
  • a cured film of the composition is formed on the Tempax glass substrate (pattern exposure is not performed), this sample is measured with a single beam, and the light transmittance at a wavelength of 400 nm per 1 ⁇ m is obtained.
  • the light transmittance of the cured film was defined as the light transmittance of the cured film.
  • Example 1 “OPTRAIK” TR-513 (trade name, catalytic conversion), which is a dispersion of 23.53 g of the polysiloxane solution (PS-1) obtained in Synthesis Example 1 and 30.4% by weight of titanium oxide-silicon oxide composite particles GBL Industrial Co., Ltd.) 30.96 g, 1.18 g of the naphthoquinonediazide compound (QD-1) obtained in Synthesis Example 14, GBL 14.45 g, DAA 12.00 g, and PGMEA 17.88 g were mixed and stirred under a yellow light. After preparing a uniform solution, it was filtered through a 0.20 ⁇ m filter to prepare Composition 1.
  • Composition 1 was spin-coated on a 6-inch silicon wafer using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) and then heated at 120 ° C. using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg Co., Ltd.). Heating for 3 minutes produced a pre-baked film having a thickness of 1.0 ⁇ m.
  • PLA PLA-501F manufactured by Canon Inc.
  • pattern exposure of the pre-baked film through a gray scale mask for sensitivity measurement using an ultra-high pressure mercury lamp followed by an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.)
  • AD-2000 manufactured by Takizawa Sangyo Co., Ltd.
  • PLA PLA (PLA-501F manufactured by Canon Inc.) was used, and the entire surface of the film was exposed to 5000 J / m 2 (wavelength 365 nm exposure amount conversion) with an ultrahigh pressure mercury lamp.
  • Table 1 shows the composition of the composition
  • Table 2 shows the evaluation results of the photosensitive characteristics and the cured film characteristics.
  • the resin composition of the present invention can provide a positive photosensitive resin composition excellent in sensitivity and resolution without impairing the properties of high refractive index and high transparency.

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Abstract

L'invention porte sur une composition de résine photosensible positive qui est caractérisée en ce qu'elle contient (a) un polysiloxane qui est synthétisé par hydrolyse et condensation partielle d'un organosilane spécifique et d'un oligomère d'organosilane, (b) des particules de composé d'aluminium, des particules de composé d'étain, des particules de composé de titane, des particules de composé de zirconium, des particules composites des composés susmentionnés ou des particules composites de l'un quelconque des composés susmentionnés et d'un composé de silicium, (c) un composé naphtoquinonediazide et (d) un solvant. La composition de résine photosensible positive est également caractérisée en ce que l'oligomère d'organosilane contient un organosilane spécifique. La composition de résine photosensible positive donne d'excellentes sensibilité et résolution sans dégradation d'un indice de réfraction élevé et d'une transparence élevée.
PCT/JP2010/066021 2009-09-29 2010-09-16 Composition de résine photosensible positive, film durci obtenu à l'aide de celle-ci et dispositif optique WO2011040248A1 (fr)

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US13/496,717 US8828642B2 (en) 2009-09-29 2010-09-16 Positive photosensitive resin composition, cured film obtained using same, and optical device
KR1020127001343A KR101726897B1 (ko) 2009-09-29 2010-09-16 포지티브형 감광성 수지 조성물, 그것을 이용한 경화막 및 광학 디바이스
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EP10820367.0A EP2485091B1 (fr) 2009-09-29 2010-09-16 Composition de résine photosensible positive, film durci obtenu à l'aide de celle-ci et dispositif optique

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